CN108217630A - A kind of preparation method and application of the Prussian blue material of composite reduction graphene oxide - Google Patents
A kind of preparation method and application of the Prussian blue material of composite reduction graphene oxide Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The present invention relates to a kind of preparation method and applications of the Prussian blue material of composite reduction graphene oxide.Preparation method be by graphene oxide ultrasonic disperse in ferrocyanide sodium water solution; ascorbic acid is added in for anti-oxidant; adding in sodium citrate reduces reaction rate; hydrochloric acid conditioning solution is added dropwise as acidity; under inert gas shielding material is obtained after heating stirring reaction; after washing, vacuum drying, microwave irradiation restores graphene oxide therein and product is made.The Prussian blue material of composite reduction graphene oxide prepared by the present invention, as sodium-ion battery anode when, substantially increase specific capacity, cycle performance and the high rate performance of battery, 153mAhg are up in organic system charging and discharging capacity‑1More than, water system list platform specific capacity 81mAhg‑1More than, preparation method is inexpensive, quick, simple, has a good application prospect.
Description
Technical field
Battery preparation technology field of the present invention, and in particular to a kind of Prussian blue material of composite reduction graphene oxide
Preparation method and application.
Background technology
Sodium-ion battery at present electrolyte, diaphragm and negative material in terms of commercial viability exposure the problem of by
Step improves, and shows excellent properties, and the progress of sodium-ion battery positive material system becomes decision battery system performance
Key factor.Positive electrode stores up sodium main part as battery, and cost occupies 28% of total cost or so, with opening for battery
It is closely bound up to send out cost, battery capacity, security performance, service life and commercial applications etc..The researcher in the field in recent years
Develop a variety of valuable positive electrode systems, educational circles's sight focuses mostly in tunnel and layered metal oxide, phosphate
The polyanionic compounds such as class and organic positive electrode and Prussian blue analogue material.
Prussian blue analogue is using a kind of important materials of rich sodium strategy support bielectron transfer, chemical formula NaxM
[Fe(CN)6]y·□1-y·nH2(transition metal ions such as M=Fe, Cu, Co, Ni, Mn, Zn, are [Fe (CN) to O6] hole)
It is above paid close attention in sodium-ion battery positive material application.This kind of complex can introduce it is a variety of change valence state transition metal from
Son, wherein Mn+/M(n+1)+, Fe2+/Fe3+The redox reaction of bielectron can be achieved, therefore its theoretical capacity can reach 180mAh
g-1.The three-dimensional framework of Prussian blue analogue (PBAs) is sometimes considered as a kind of metal-organic framework, and the basic ion larger for volume carries
PBAs is made to become the excellent positive electrode that one kind has extended cycle life, electric charge transfer is fast for big channel.And Prussian blue analogue material
Environmental-friendly, resourceful, preparation simplicity, shows good industrial applications prospect.
The theoretical specific capacity of Prussian blue electrode material is up to nearly 180mAh/g, but in actual use, and specific capacity is not to the utmost
People's will, and the material electric conductivity is bad, has seriously affected its further applying as sodium-ion battery positive material.Cause
How this, improve capacity and high rate performance of the Prussian blue material when being applied as sodium-ion battery positive material, be always
The focus on research direction of those skilled in the art.
Current most common solution is to introduce the better carbon material of electric conductivity, adulterates or coats such as in positive electrode
Carbon material etc., and then the resistance between each component is reduced, improve the conductivity and high rate performance of Prussian blue analogue.Patent document report
Prussian blue analogues/the carbon material for preparing in road mainly includes：" a kind of novel high-performance composite nanometer material is repaiied for Jilin University
Adorn the preparation method of electrode " (CN101792137A)；A kind of Lanzhou University's " the Prussian blue complexs of nano Co-Fe-carbon nanometer
Manage the preparation method of compound hydrogen peroxide sensor " (CN102175728A)；" graphene/prussian blue is matched for Beijing Institute of Technology
Close object composite aerogel, preparation method and application " (CN102824883A) and Wuhan University's " a kind of sodium-ion battery anode material
Material " (CN102522553A).However the these preparation methods reported at present are mostly prepared using solution coprecipitation, it is prepared by this method
Crystal structure it is not perfect, internal vacancy and the crystallization water and coordination water content are more, make to show during sodium-ion battery positive material
Go out relatively low capacity and the cycle performance of difference.And the recombination process of carbon is mostly by first synthesizing Prussian blue material again by itself and carbon
Material simple physical mixes, and Prussian blue in this way to be contacted well with carbon material, the battery performance under high magnification is bad, and
Method is complicated for operation, it is of high cost, can not achieve quick preparation.
Invention content
(1) technical problems to be solved
In order to solve the above problem of the prior art, the present invention provides a kind of the Prussian blue of composite reduction graphene oxide
The preparation method of material, a kind of Prussian blue material of composite reduction graphene oxide prepared by this method overcome existing general Shandong
Scholar's blue material is poor there are high rate performance when being applied as sodium-ion battery positive material, and specific capacity is low and method is of high cost, grasps
Make the defects of complicated.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include：
A kind of preparation method of the Prussian blue material of composite reduction graphene oxide, is by graphene oxide ultrasonic disperse
In ferrocyanide sodium water solution, ascorbic acid is added in for anti-oxidant, adding in sodium citrate reduces reaction rate, and hydrochloric acid is added dropwise
Solution is adjusted as acidity, obtains material after heating stirring reaction under inert gas shielding, after washing, vacuum drying, microwave spoke
Product is made according to graphene oxide therein is restored.
Preparation method as described above, specifically, this method comprises the following steps：
S1, Na is prepared4Fe(CN)6Water solution A, adds in graphene oxide, and ultrasound makes graphene oxide be uniformly dispersed to obtain
Solution B,
S2, ascorbic acid and sodium citrate are added in into the solution B, stirs to get mixed solution C；
S3, acidity is adjusted to mixed solution C dropwise addition hydrochloric acid, obtains solution D；
S4, the solution D is placed in water bath with thermostatic control, is passed through inert gas, is protected from light；
S5, by the step S4 react after mixed solution, be placed in room temperature, be aged under the conditions of being protected from light；
S6, the mixed solution after step S5 ageings is subjected to separation of solid and liquid, washing obtains solid product E；
S7, by the solid product E, dry under vacuum, obtain product F；
S8, the product F is subjected to microwave reduction graphene oxide, obtains the Prussian blue of composite reduction graphene oxide
Material.
Preparation method as described above, it is preferable that in step sl, the Na4Fe(CN)6A concentration of the 10 of solution~
30mmol/L, the graphene oxide press the Na4Fe(CN)61%~10% addition of quality, the time of the ultrasound is 10
~30min, ultrasonic frequency are 40~60KHz.
Preparation method as described above, it is preferable that in step s 2, the ascorbic acid and sodium citrate are in the solution
Final concentration of 1~5mmol/L in C；In step s 2, the acidity refers to that the pH value of mixed solution C is 0.5~1.5.
Preparation method as described above, it is preferable that in step s 4, the temperature of the water bath with thermostatic control is controlled 60~80
DEG C, the time being protected from light is 3~6h, and the inert gas is the mixing of nitrogen, hydrogen, argon gas or above-mentioned several gases
Gas.
Preparation method as described above, it is preferable that in step s 5, the time of the ageing is for 24 hours~72h.
Preparation method as described above, it is preferable that in step s 6, for the separation of solid and liquid using centrifuging, centrifugation is fast
It spends for 7000~10000rpm；The washing is cleaned 2~4 times for water, then with washes of absolute alcohol 1~3 time.
Preparation method as described above, it is preferable that in the step s 7, the temperature of the drying is 80~120 DEG C, and the time is
24~48h.
Preparation method as described above, it is preferable that in step s 8, the power of the microwave reduction is 500~1000w,
1~10s of exposure time.
Preparation method as described above, it is preferable that the Pu Lu for the composite reduction graphene oxide that the preparation method obtains
Scholar's blue material is represented by Na2FeFe(CN)6@rGO, grain size are 200~800nm.
The Prussian blue material of composite reduction graphene oxide that preparation method as described above prepares in battery just
Application in the material of pole.
Application as described above, it is preferable that the Prussian blue material of the composite reduction graphene oxide, with carbon black and viscous
Agent is tied with mass ratio 80：10：10 mixing are made into slurry, are homogeneously applied on collector, dry and obtain cell positive material.
(3) advantageous effect
The beneficial effects of the invention are as follows：
The preparation method of the Prussian blue material of composite reduction graphene oxide of the present invention is the base in solution coprecipitation
It is improved on plinth, using product Na2FeFe(CN)6The source of middle Fe is only from Na4Fe(CN)6This kind of solution, by adding
Enter ascorbic acid (VC) and the protection of logical nitrogen occupies the combination water of lattice position, and then promote class to promote sodium content and then squeeze out
Therefore the specific capacity of Shandong scholar indigo plant, cyclical stability are also improved.
The present invention adds in reaction suppressor during the reaction, and sodium citrate carrys out reaction speed.Citric acid can be with
Transition metal ions combines, and so as to reduce the nucleation rate of iron cyanide and iron ion, the competition of two kinds of ligands in the solution is closed
System reduces vacancy and Interstitial Water and quantity, and material has higher crystallinity, regular pattern, and therefore its specific capacity also obtains
To improvement.
Preparation method of the present invention is simple for process, reagent is used to be easy to get, operating condition is easy to implement, manufacturing cost
It is low, quick, simple.The material electrochemical performance of preparation is excellent, has higher specific capacity, cycle performance and high rate performance,
Organic system charging and discharging capacity is up to 153mAhg-1More than, water system list platform specific capacity 81mAhg-1More than, safely may be used
It leans on, has a good application prospect.
Description of the drawings
Fig. 1 is Na prepared by comparative example2FeFe(CN)6(PB) SEM is schemed with preparing material (rGOPB) in embodiment 1
SEM schemes, wherein, (a) PB, X5000；(b) PB, X20000；(c) rGOPB, X5000；(d) rGOPB, X20000；
Fig. 2 is the charging and discharging curve comparison diagram for the material that embodiment 1 is prepared with comparative example；
Fig. 3 is the high rate performance comparison diagram after the material that embodiment 1 is prepared with comparative example；
Fig. 4 is charging and discharging curve of the material prepared in embodiment 2 in water system battery.
Specific embodiment
The technical problems to be solved by the invention be to overcome existing Prussian blue material as sodium-ion battery just
There are the defects of conductivity is bad, high rate performance is poor, specific capacity is low during the application of pole material, in preparation method：
(1) raw material uses sodium ferrocyanide Na4Fe(CN)6, other Fe sources is not used to supply, such as FeCl3Solution.Because of Na4Fe
(CN)6In Fe (CN)6 4-It can be decomposed in suitable pH environment and generate Fe2+, Fe2+Easily it is oxidized to Fe3+, Fe3+And Fe2+It will be with remaining
Remaining Fe (CN)6 4-Reaction bonded generates blue precipitate Prussian blue analogue.
(2) using ascorbic acid (VC) and logical inert gas shielding in the present invention.Due to Fe2+It is oxidizable, in antioxidant
And under logical inert gas, effectively avoid Fe2+It is aoxidized.Ascorbic acid can with reference to oxygen and as oxygen scavenger, and have passive metal from
The oxygen in solution is discharged and has been completely cut off in the effect of son, being introduced into for inert gas.If ferrous iron part is oxidized to ferric iron,
The average valence raising of iron, represent its it is corresponding can embedding de- sodium content it is low, and sodium is in the lattice frame, and sodium content reduces meaning
Taste the increase for the combination water for occupying lattice position, adds in ascorbic acid (VC) and logical nitrogen is protected to promote sodium content and then squeeze
Fall to occupy the combination water of lattice position, and then promote the specific capacity of class Shandong scholar indigo plant, therefore cyclical stability is also improved.
3) sodium citrate is employed in the method for the present invention.Since the crystalline quality of Prussian blue analogue is related to nucleation rate,
The citric acid of addition can be combined with transition metal ions, and so as to reduce the nucleation rate of iron cyanide and iron ion, two kinds are matched
The competitive relation of body in the solution reduces vacancy and Interstitial Water and quantity.Material has higher crystallinity, regular pattern, and
Therefore its specific capacity is also improved.
4) present invention is using In-situ reaction graphene oxide, since graphene oxide (GO) has good hydrophily,
It is uniformly dispersed in the solution under the action of ultrasound, the Prussian blue particle formed in reaction process can be attached on GO networks
Crystallization nucleation is closely contacted with carbon material.Due to GO limited electrical conductivities, rGO (redox graphene) is reduced to, is made
Material electric conductivity increases, and high rate performance is significantly improved.
In the prior art using high temperature reduction method, this method is with high costs and the reaction time is more long, with Prussian blue material
The characteristic of material is away from each other.The present invention, which is worked out, using cheap, quick microwave irradiation reduction method, obtains new Material cladding reduction
The Prussian blue material of graphene oxide, can be used chemical formula Na2FeFe(CN)6@rGO are represented, according to ICP- in actual test
AES measures Fe, Na constituent content, and EA measures C, N element, TGA test water contents, and material true chemical is configured to Na1.51Fe[Fe
(CN)6]0.89□0.11·4.98H2O (=Fe (CN)6Hole), wherein the ratio 1%-10% of compound rGO is differed.It is forthright again
Energy, cycle performance and specific capacity all greatly promote.
Preparation method of the present invention is raw materials used to be easy to get, is easy to operate, device therefor easy realization at low cost, integral manufacturing cost
Effectively reduce, it is quick.
In order to preferably explain the present invention, in order to understand, below in conjunction with the accompanying drawings, by specific embodiment, to this hair
It is bright to be described in detail.
Embodiment 1
The preparation method of the Prussian blue material of composite reduction graphene oxide, using following steps：
1) Na of a concentration of 10mM of 200ml is prepared4Fe(CN)6Solution A is transferred them in the beaker of magneton, and magnetic force stirs
Mix device slow-speed of revolution 300rpm stirrings.2) commercially available graphene oxide GO is used, by opposite Na4Fe(CN)6Quality proportioning 2% claim
Amount is added in solution A, and ultrasonic 10min makes it be uniformly dispersed to obtain solution B.
3) ascorbic acid for making its final concentration of 1mM and 1mM sodium citrates are added in solution B, stirring 5min is mixed
Solution C.
4) using the pH value of pH tester real-time testing solution Cs, hydrochloric acid is added dropwise to pH=1, obtains solution D.
5) above-mentioned solution D is transferred to flask and be fixed in water-bath, lead to inert gas such as nitrogen, avoid light place will
Solution is stirred in 60 DEG C of constant temperature 3.5h under protective atmosphere, stir speed (S.S.) 400rpm.
6) mixed solution after being stirred to react is aged for 24 hours under the conditions of room temperature is protected from light.
7) mixed solution being aged is subjected to separation of solid and liquid, and will first be obtained with water with the centrifugal speed of 7000rpm
Solid cleans 2 times, then with washes of absolute alcohol 2 times to supernatant pH=7, obtains clean solid product E.
8) clean solid product E under 80 DEG C of vacuum conditions is dried into 48h, obtains product F.
9) product F is ground into 10min, grinding is for dispersion, does not change grain size, after grinding and paves and is transferred to
In flat culture dish, progress microwave reduction graphene oxide in micro-wave oven is put into, setting power is 500w, exposure time 5s, is incited somebody to action
Graphene oxide (GO) in material F is reduced to reduced graphene (rGO), finally obtains final product G needed for the present invention, is deep
Blue powder (navy blue is due to introducing carbon), is represented by Na2FeFe(CN)6@rGO。
Comparative example
Using method as described above, graphene oxide dosage as a comparison, prepares the Prussian blue of pure phase for 0
Na2FeFe(CN)6It is abbreviated as PB.
By Na manufactured in the present embodiment1.4FeFe(CN)6@rGO and existing pure phase Na2FeFe(CN)6Material SEM figure with
Material Na2FeFe(CN)6The SEM figures of@rGO are as shown in Figure 1, wherein (a), (b) are that the PB that respectively prepared by comparative example is in resolution ratio
SEM figures under 5000 and 20000, (c), (d) are respectively Na prepared by embodiment 11.4FeFe(CN)6@rGO are abbreviated as rGOPB,
SEM figures under being 5000 and 20000 in resolution ratio.By in figure, it can be seen that material particle size prepared by embodiment 1 for 200~
800nm, crystal particle diameter do not change, and regularity is slightly decreased, Prussian blue that clearly graphene stratiform carbon can be seen therebetween
Web frame illustrates that carbon complication experiment is relatively more successful.
Embodiment 2
The preparation method of the Prussian blue material of composite reduction graphene oxide, includes the following steps：
1) Na of a concentration of 20mM of 200ml is prepared4Fe(CN)6Solution A is transferred them in the beaker of magneton, and magnetic force stirs
Mix device slow-speed of revolution stirring.
2) pre-prepared graphene oxide GO is shifted to an earlier date using Hummers methods, by opposite Na4Fe(CN)6Quality proportioning 5% claim
Amount is added in solution A, and ultrasonic 15min makes it be uniformly dispersed to obtain solution B.
3) adding in ascorbic acid and sodium citrate to solution B makes its final concentration be respectively 2.5mM, and stirring 8min is mixed
Close solution C.
4) using the pH value of pH tester real-time testing solution Cs, hydrochloric acid is added dropwise to pH=1.2, obtains solution D.
5) above-mentioned solution D is transferred to flask and be fixed in water-bath, lead to inert gas such as nitrogen or the mixing of hydrogen argon gas
Gas, avoid light place, by solution in 70 DEG C of heated at constant temperature 5h, the 600r/min stirrings under protective atmosphere.
6) mixed solution after being stirred to react is aged 48h under the conditions of room temperature is protected from light.
7) mixed solution being aged is subjected to separation of solid and liquid, and will first be obtained with water with the centrifugal speed of 8000rpm
Solid cleans 2 times, then with washes of absolute alcohol 3 times, obtains clean solid product E.
8) clean solid product E more than drying for 24 hours, is obtained into product F under 100 DEG C of vacuum conditions.
9) product F is ground 15min and paved and be transferred in flat culture dish, be put into progress microwave reduction oxygen in micro-wave oven
Graphite alkene, setting power are 800w, exposure time 2s, and the GO in material F is reduced to rGO, is finally obtained needed for the present invention
Final product G.
Embodiment 3
The preparation method of the Prussian blue material of composite reduction graphene oxide, includes the following steps：
1) Na of a concentration of 30mM of 200ml is prepared4Fe(CN)6Solution A is transferred them in the beaker of magneton, and magnetic force stirs
Mix device slow-speed of revolution stirring.
2) pre-prepared graphene oxide GO is shifted to an earlier date using Hummers methods, by opposite Na4Fe(CN)6Quality proportioning 10% claim
Amount is added in solution A, and ultrasonic 30min makes it be uniformly dispersed to obtain solution B.
3) ascorbic acid for making final concentration of 5mM and 5mM sodium citrates are added in solution B, stirring 10min obtains mixing molten
Liquid C.
4) using the pH value of pH tester real-time testing solution Cs, hydrochloric acid is added dropwise to pH=2, obtains solution D.
5) above-mentioned solution D is transferred to flask and be fixed in water-bath, lead to inert gas such as nitrogen or the mixing of hydrogen argon gas
Gas, avoid light place, by solution in 80 DEG C of heated at constant temperature 3h, the 800r/min stirrings under protective atmosphere.
6) mixed solution after being stirred to react is aged 72h under the conditions of room temperature is protected from light.
7) mixed solution being aged is subjected to separation of solid and liquid, and first will with water with the centrifugal speed of 10000rpm/min
It obtains solid to clean 4 times, then with washes of absolute alcohol 1 time, obtains clean solid product E.
8) by clean solid product E, drying for 24 hours, obtains product F under 120 DEG C of vacuum conditions.9) product F is ground
15min and paving is transferred in flat culture dish, is put into progress microwave reduction graphene oxide in micro-wave oven, and setting power is
GO in material F is reduced to rGO, finally obtains final product G needed for the present invention by 1000w, exposure time 1s.
Embodiment 4
Organic system battery is prepared, with the following method：
1) material G, carbon black and the PVDF binding agents embodiment 1 being prepared are with mass ratio 80：10：10 mixing are with slurry
Material, is homogeneously applied to obtain working electrode in aluminum foil current collector.
2) using sodium sheet metal as to electrode, glass fibre membrane is as diaphragm, 1mol/L NaClO4(solvent is volume
Than 1：1 ethylene carbonate and dimethyl carbonate mixed liquor) as electrolyte, it is assembled in glove box and obtains Swagelok types electricity
Pond.
The battery of above-mentioned assembling is subjected to charge-discharge test on LAND charge-discharge test instrument.Charge and discharge result such as Fig. 2 institutes
Show, wherein, PB is material prepared by comparative example, and rGOPB is product G prepared by embodiment 1.Current density 0.1C, voltage range
As a result 2.0-4.0V illustrates the Prussian blue material of composite reduction graphene oxide of the invention prepared than Prussian blue charge and discharge
Electric specific capacity is promoted notable.First charge-discharge specific capacity is from 130mAh g-1Increase to 153mAh g-1。
The results are shown in Figure 3 for high rate performance, and high rate performance has tremendous increase after showing composite carbon.As organic system electricity
Pond has a wide range of applications in terms of power battery.
Embodiment 5
Aqueous systems battery is prepared, with the following method：
1) material G, carbon black and the PTFE binding agents embodiment 2 being prepared are with mass ratio 80：10：10 mixing are with slurry
Material, and carry out dispersed actives using isopropanol, finally obtain doughy dark blue mixture.Collector uses nickel foam generation
For aluminium foil, by the film compacting rolled on nickel foam.
2) it is done using vitreous carbon to electrode, the positive electrode of above-mentioned drying is clamped on metal, rod-shaped fixture.It uses
2molL is configured in 250ml volumetric flasks-1Na2SO4Solution.Electrolyte is added, it is made two electrode areas for not being coated with slurry.It will
Saturation KCl liquid is added to suitable position in reference electrode, makes its end as possible close to without contacting active electrode.Logical nitrogen removes
Oxygen 5min, adding in atoleine makes it cover electrolyte surface.
3) LAND battery test system setup tests are accessed after screwing hermetic.Wherein organic system test is directly consolidated using clip
Fixed, water system battery lead conducting wire connects corresponding electrode.
Charging and discharging curve is as shown in figure 4, result illustrates the capacity 81mAh g of low-voltage list platform-1, hence it is evident that higher than existing skill
Lead-acid battery 30-40mAh g in art-1, therefore its as to energy density water system battery of less demanding on a large scale could field
There is good application prospect.
The above described is only a preferred embodiment of the present invention, being not the limitation that other forms are done to the present invention, appoint
What those skilled in the art can be changed or be modified as the equivalence enforcement of equivalent variations using technology contents disclosed above
Example.But it is every without departing from technical solution of the present invention content, technical spirit according to the present invention is appointed to what above example was made
What simple modification, equivalent variations and remodeling still falls within the protection domain of technical solution of the present invention.
Claims (10)
1. a kind of preparation method of the Prussian blue material of composite reduction graphene oxide, which is characterized in that the preparation method is
By graphene oxide ultrasonic disperse in ferrocyanide sodium water solution, ascorbic acid is added in for anti-oxidant, addition sodium citrate
Reaction rate is reduced, hydrochloric acid conditioning solution is added dropwise as acidity, obtains material after heating stirring reaction under inert gas shielding, washes
After washing, being dried in vacuo, microwave irradiation restores graphene oxide therein and product is made.
2. preparation method as described in claim 1, which is characterized in that preparation method specifically comprises the following steps：
S1, Na is prepared4Fe(CN)6Solution A, adds in graphene oxide, and ultrasound makes graphene oxide be uniformly dispersed to obtain solution B；
S2, ascorbic acid and sodium citrate are added in into the solution B, stirs to get mixed solution C；
S3, acidity is adjusted to mixed solution C dropwise addition hydrochloric acid, obtains solution D；
S4, the solution D is placed in water bath with thermostatic control, is passed through inert gas, is protected from light；
S5, by the step S4 react after mixed solution, be placed in room temperature, be aged under the conditions of being protected from light；
S6, the mixed solution after step S5 ageings is subjected to separation of solid and liquid, washing obtains solid product E；
S7, by the solid product E, dry under vacuum, obtain product F；
S8, the product F is subjected to microwave reduction graphene oxide, obtains the Prussian blue material of composite reduction graphene oxide
Material.
3. preparation method as claimed in claim 2, which is characterized in that in step sl, the Na4Fe(CN)6The concentration of solution
For 10~30mmol/L, the graphene oxide presses the Na4Fe(CN)6Quality 1%~10% addition, it is described ultrasound when
Between for 10~30min, ultrasonic frequency is 40~60KHz.
4. preparation method as claimed in claim 2, which is characterized in that in step s 2, the ascorbic acid and sodium citrate
Final concentration of 1~5mmol/L in the solution C；In step s 2, the acidity refers to that the pH value of mixed solution C is 0.5
~1.5.
5. preparation method as claimed in claim 2, which is characterized in that in step s 4, the temperature control of the water bath with thermostatic control
At 60~80 DEG C, the time being protected from light is 3~6h, and the inert gas is any one of nitrogen, hydrogen or argon gas
Or more than one mixed gas；
In step s 5, the time of the ageing is for 24 hours~72h.
6. preparation method as claimed in claim 2, which is characterized in that in step s 6, the separation of solid and liquid is using centrifugation point
From centrifugal speed is 7000~10000rpm；The washing is cleaned 2~4 times for water, then with washes of absolute alcohol 1~3 time.
7. preparation method as claimed in claim 2, which is characterized in that in the step s 7, the temperature of the drying is 80~120
DEG C, the time is 24~48h.
8. preparation method as claimed in claim 2, which is characterized in that in step s 8, the power of the microwave reduction is 500
~1000w, 1~10s of exposure time.
9. the preparation method as described in any one of claim 1-8, which is characterized in that prepare the composite reduction oxidation
The grain size of the Prussian blue material of graphene is 200~800nm.
10. the composite reduction graphene oxide that the preparation method as described in any one of claim 1-8 obtains is Prussian blue
Application of the material in cell positive material.
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